U.S. patent number 7,314,903 [Application Number 10/520,565] was granted by the patent office on 2008-01-01 for catalyst system for the polymerization of olefins.
This patent grant is currently assigned to Basell Polyolefine GmbH. Invention is credited to Isabella Camurati, Francesca Focante, Simona Guidotti, Luigi Resconi.
United States Patent |
7,314,903 |
Resconi , et al. |
January 1, 2008 |
**Please see images for:
( Certificate of Correction ) ** |
Catalyst system for the polymerization of olefins
Abstract
An organometallic compound obtainable by contacting: a compound
having the following formula (I), wherein: R.sup.a is a hydrocarbon
radical; R.sup.b, R.sup.c and R.sup.d, are hydrogen atoms, halogen
atoms, or hydrocarbon radicals; with a Lewis acid of formula (II)
MtR.sup.1.sub.3 (II) wherein Mt is a metal belonging to Group 13 of
the Periodic Table of the Elements; R.sup.1 are selected from the
group consisting of halogen atoms, halogenated C.sub.6 C.sub.20
aryl and halogenated C.sub.7 C.sub.20 alkylaryl groups
##STR00001##
Inventors: |
Resconi; Luigi (Ferrara,
IT), Focante; Francesca (Filottrano, IT),
Camurati; Isabella (Ferrara, IT), Guidotti;
Simona (Altedo-Malalbergo, IT) |
Assignee: |
Basell Polyolefine GmbH
(Wesseling, DE)
|
Family
ID: |
30115746 |
Appl.
No.: |
10/520,565 |
Filed: |
July 9, 2003 |
PCT
Filed: |
July 09, 2003 |
PCT No.: |
PCT/EP03/07485 |
371(c)(1),(2),(4) Date: |
January 07, 2005 |
PCT
Pub. No.: |
WO2004/005360 |
PCT
Pub. Date: |
January 15, 2004 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20060094840 A1 |
May 4, 2006 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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60394614 |
Jul 9, 2002 |
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Current U.S.
Class: |
526/134; 502/103;
502/123; 502/152; 502/167; 526/133; 526/139; 526/141; 526/160;
526/161; 526/172 |
Current CPC
Class: |
C07F
5/027 (20130101); C08F 10/00 (20130101); C08F
10/00 (20130101); C08F 4/65908 (20130101); C08F
4/65912 (20130101); C08F 4/65925 (20130101); C08F
110/02 (20130101) |
Current International
Class: |
C08F
4/70 (20060101) |
Field of
Search: |
;526/133,134,160,161,172,139,141 ;502/103,123,167,152 |
References Cited
[Referenced By]
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WO |
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May 1999 |
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WO |
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9964476 |
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Dec 1999 |
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WO |
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0162764 |
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Aug 2001 |
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WO |
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Other References
B Temme et al., "Oxidative .eta..sup.2-iminoacyl formation by
reaction of amidozirconocene complexes with
tris(pentafluorophenyl)borane," Journal of Organometallic
Chemistry, vol. 488, p. 177-182 (1995). cited by other .
M. Brookhart et al., "Highly Active Iron and Cobalt Catalysts for
the Polymerization of Ethylene," J. Am. Chem. Soc., vol. 120, p.
4049-4050 (1998). cited by other .
M. Brookhart et al., "New Pd(II)- and Ni(II)-Based Catalysts for
Polymerization of Ethylene and .alpha.-Olefins," J. Am. Chem. Soc.,
vol. 117(23), p. 6414-6415 (1995). cited by other .
M. Brookhart et al,. "Copolymerization of Ethylene and Propylene
with Functionalized Vinyl Monomers by Palladium(II) Catalysts," J.
Am. Chem. Soc., vol. 118, p. 267-268 (1996). cited by other .
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iron and cobalt," Chem. Commun., p. 849-851 (1998). cited by other
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Zirconium; Synthesis, Structure and Polymerization Studies," Chem.
Ber./Recueil, vol. 130, p. 399-403 (1997). cited by other .
Bernd Wrackmeyer et al., "Nuclear magnetic resonance studies on
boron compounds, X. Boron-11, nitrogen-14 and proton NMR studies on
boryl-substituted thiophene, furan, and N-methylpyrrole and related
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Database Caplus, Chemical Abstracts Service, Columbus, Ohio, Tadami
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No. 70:88432 (abstract). cited by other .
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accession No. 71:22482 (abstract). cited by other.
|
Primary Examiner: Lu; Caixia
Attorney, Agent or Firm: Raphael; Jarrod N
Parent Case Text
This application is the U.S. national phase of International
Application PCT/EP2003/007485, filed Jul. 9, 2003, claiming the
benefit under 35 U.S.C. 119(e) of U.S. Provisional Application No.
60/394,614, filed Jul. 9, 2002; the disclosures of International
Application PCT/EP2003/007485, and U.S. Provisional Application No.
60/394,614, each as filed, are incorporated herein by reference.
Claims
The invention claimed is:
1. An organometallic compound obtained by contacting: a) a compound
having the following formula (I): ##STR00023## wherein R.sup.a is a
linear or branched, saturated or unsaturated, C.sub.1 C.sub.10
alkyl, C.sub.6 C.sub.20 aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7
C.sub.20 alkylaryl group, optionally containing O, S, N, P, Si or
halogen atoms; or R.sup.a can join R.sup.d to form a C.sub.4
C.sub.7 ring; R.sup.b, R.sup.c and R.sup.d, equal to or different
from each other, are hydrogen atoms, halogen atoms, linear or
branched, saturated or unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6
C.sub.20 aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7 C.sub.20
alkylaryl groups, optionally containing O, S, N, P, Si or halogen
atoms, or two or more adjacent substituents R.sup.b, R.sup.c, and
R.sup.d form one or more C.sub.4 C.sub.7 rings, optionally
containing O, S, N, P or Si atoms, that can bear substituents; with
b) a Lewis acid of formula (II): MtR.sup.1.sub.3 (II) wherein Mt is
a metal belonging to Group 13 of the Periodic Table of the
Elements; R.sup.1, equal to or different from each other, are
halogen atoms, halogenated C.sub.6 C.sub.20 aryl or halogenated
C.sub.7 C.sub.20 alkylaryl groups; two R.sup.1 groups can also form
with the metal Mt one condensed ring.
2. The organometallic compound according to claim 1 wherein Mt is B
or Al; and the substituents R.sup.1 are C.sub.6F.sub.5,
C.sub.6F.sub.4H, C.sub.6F.sub.3H.sub.2,
C.sub.6H.sub.3(CF.sub.3).sub.2, perfluoro-biphenyl,
heptafluoro-naphthyl, hexafluoro-naphthyl or
pentafluoro-naphthyl.
3. The organometallic compound according to claim 1 having formula
(III): ##STR00024## wherein Mt is a metal belonging to Group 13 of
the Periodic Table of the Elements (IUPAC); R.sup.1, equal to or
different from each other, are halogen atoms, halogenated C.sub.6
C.sub.20 aryl or halogenated C.sub.7 C.sub.20 alkylaryl groups; or
two R.sup.1 groups can form with the metal Mt one condensed ring;
the substituents R.sup.5, R.sup.4 and R.sup.3 equal to or different
from each other, are hydrogen atoms, halogen atoms, linear or
branched, saturated or unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6
C.sub.20 aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7 C.sub.20
alkylaryl groups, optionally containing O, S, N, P, Si or halogen
atoms, or two or more adjacent substituents R.sup.3, R.sup.4 and
R.sup.5 form one or more C.sub.4 C.sub.7 rings, optionally
containing O, S, N, P or Si; R.sup.2 is a linear or branched,
saturated or unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6 C.sub.20
aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7 C.sub.20 alkylaryl
group, optionally containing O, S, N, P, Si or halogen atoms or
R.sup.2 can join R.sup.5 to form a C.sub.4 C.sub.7 ring.
4. The organometallic compound according to claim 3 wherein Mt is B
or Al; the substituents R.sup.1, equal to or different from each
other, are C.sub.6F.sub.5, C.sub.6F.sub.4H, C.sub.6F.sub.3H.sub.2,
C.sub.6H.sub.3(CF.sub.3).sub.2, perfluoro-biphenyl,
heptafluoro-naphthyl, hexafluoro-naphthyl or pentafluoro-naphthyl;
R.sup.4 and R.sup.5 form one C.sub.5 C.sub.6 aromatic ring,
optionally containing O, S, N, or P atoms, that can bear
substituents; R.sup.2 is a C.sub.1 C.sub.10 alkyl or C.sub.6
C.sub.20 aryl group; and R.sup.3 is hydrogen.
5. The organometallic compound according to claim 3 having formula
(V): ##STR00025## wherein B is a boron atom; the substituents
R.sup.6, the same or different from each other, are hydrogen atoms,
halogen atoms, linear or branched, saturated or unsaturated,
C.sub.1 C.sub.10 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7 C.sub.20
arylalkyl or C.sub.7 C.sub.20 alkylaryl groups optionally
containing O, S, N, P, Si or halogen atoms, or two or more adjacent
substituents R.sup.6 form one or more C.sub.4 C.sub.7, optionally
containing O, S, N, P or Si atoms rings that can bear
substituents.
6. The organometallic compound according to claim 1 having formula
(IV): ##STR00026## wherein the substituents R.sup.3', R.sup.4' and
R.sup.5', equal to or different from each other, are hydrogen
atoms, halogen atoms, linear or branched, saturated or unsaturated,
C.sub.1 C.sub.10 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7 C.sub.20
arylalkyl or C.sub.7 C.sub.20 alkylaryl groups, optionally
containing O, S, N, P, Si or halogen atoms, or two or more adjacent
substituents R.sup.3', R.sup.4' and R.sup.5' form one or more
C.sub.4 C.sub.7 rings, optionally containing O, S, N, P or Si
atoms, that can bear substituents; said rings can be aliphatic and
optionally contain double bonds; with the proviso that said rings
are not aromatic; R.sup.2' is a linear or branched, saturated or
unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7
C.sub.20 arylalkyl or C.sub.7 C.sub.20 alkylaryl group, optionally
containing O, S, N, P, Si or halogen atoms; or R.sup.2' can join
R.sup.5' to form a C.sub.4 C.sub.7 ring.
7. The organometallic compound according to claim 6 wherein
R.sup.2' is a C.sub.1 C.sub.10 alkyl, or C.sub.6 C.sub.20 aryl
group; the substituents R.sup.3', R.sup.4' and R.sup.5', equal to
or different from each other, are hydrogen atoms, linear or
branched, saturated or unsaturated, C.sub.1 C.sub.10 alkyl,
optionally containing O, S, N, P, Si or halogen atoms, or two or
more adjacent substituents R.sup.3', R.sup.4' and R.sup.5' form one
or more C.sub.4 C.sub.7 rings optionally containing O, S, N, P or
Si atoms, that can bear substituents; said rings can be aliphatic
and optionally contain double bonds, with the proviso that said
rings are not aromatic.
8. The organometallic compound according to claim 6 having formula
(VI): ##STR00027## wherein the substituent R.sup.5' is a C.sub.1
C.sub.20 alkyl group.
9. A salt obtained by contacting, in any order: a) a compound
having formula (I): ##STR00028## wherein R.sup.a is a linear or
branched, saturated or unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6
C.sub.20 aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7 C.sub.20
alkylaryl group, optionally containing O, S, N, P, Si or halogen
atoms; or R.sup.a can join R.sup.d to form a C.sub.4 C.sub.7 ring;
R.sup.b, R.sup.c and R.sup.d, equal to or different from each
other, are hydrogen atoms, halogen atoms, linear or branched,
saturated or unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6 C.sub.20
aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7 C.sub.10 alkylaryl
groups, optionally containing O, S, N, P, Si or halogen atoms, or
two or more adjacent substituents R.sup.b, R.sup.c, and R.sup.d
form one or more C.sub.4 C.sub.7 rings, optionally containing O, S,
N, P or Si atoms, that can bear substituents; b) a Lewis acid of
formula (II): MtR.sup.1.sub.3 (II) wherein Mt is a metal belonging
to Group 13 of the Periodic Table of the Elements; R.sup.1, equal
to or different from each other, are halogen atoms, halogenated
C.sub.6 C.sub.20 aryl or halogenated C.sub.7 C.sub.20 alkylaryl
groups; two R.sup.1 groups can also form with the metal Mt one
condensed ring; and c) a compound of formula KR.sup.f.sub.3 wherein
K is a nitrogen (N) or phosphorous (P) atom; R.sup.f, equal to or
different from each other, are linear or branched, saturated or
unsaturated, C.sub.1 C.sub.30 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7
C.sub.20 arylalkyl or C.sub.7 C.sub.20 alkylaryl groups, optionally
containing O, S, N, P, Si or halogen atoms, or two R.sup.f can form
one C.sub.4 C.sub.7 ring, optionally containing O, S, N, P or Si
atoms, that can bear substituents.
10. The salt according to claim 9 wherein K is nitrogen; and
R.sup.f is selected from the group consisting of linear or
branched, saturated or unsaturated, C.sub.1 C.sub.30 alkyl.
11. The salt according to claim 9 having formula (VII):
##STR00029## wherein R.sup.1, equal to or different from each
other, are halogen atoms, halogenated C.sub.6 C.sub.20 aryl or
halogenated C.sub.7 C.sub.20 alkylaryl groups; or two R.sup.1
groups can form with the metal Mt one condensed ring; the
substituents R.sup.5, R.sup.4 and R.sup.3, equal to or different
from each other, are hydrogen atoms, halogen atoms, linear or
branched, saturated or unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6
C.sub.20 aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7 C.sub.20
alkylaryl groups, optionally containing O, S, N, P, Si or halogen
atoms, or two or more adjacent substituents R.sup.3, R.sup.4 and
R.sup.5 form one or more C.sub.4 C.sub.7 rings, optionally
containing O, S, N, P or Si; R.sup.2 is a linear or branched,
saturated or unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6 C.sub.20
aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7 C.sub.10 alkylaryl
group, optionally containing O, S, N, P, Si or halogen atoms or
R.sup.2 can join R.sup.5 to form a C.sub.4 C.sub.7 ring.
12. The salt according to claim 11 having formula (IX):
##STR00030## wherein B is a boron atom.
13. The salt according to claim 9 having formula (VIII):
##STR00031## wherein R.sup.1, equal to or different from each
other, are halogen atoms, halogenated C.sub.6 C.sub.20 aryl or
halogenated C.sub.7 C.sub.10 alkylaryl groups; two R.sup.1 groups
can also form with the metal Mt one condensed ring; the
substituents R.sup.3', R.sup.4' and R.sup.5', equal to or different
from each other, are hydrogen atoms, halogen atoms, linear or
branched, saturated or unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6
C.sub.20 aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7 C.sub.20
alkylaryl groups, optionally containing O, S, N, P, Si or halogen
atoms, or two or more adjacent substituents R.sup.3', R.sup.4' and
R.sup.5' form one or more C.sub.4 C.sub.7 rings, optionally
containing O, S, N, P or Si atoms, that can bear substituents; said
rings can be aliphatic and optionally contain double bonds; with
the proviso that said rings are not aromatic; R.sup.2' is a linear
or branched, saturated or unsaturated, C.sub.1 C.sub.10 alkyl,
C.sub.6 C.sub.20 aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7
C.sub.20 alkylaryl group, optionally containing O, S, N, P, Si or
halogen atoms; or R.sup.2' can join R.sup.5' to form a C.sub.4
C.sub.7 ring.
14. The salt according to claim 13 having formula (X): ##STR00032##
wherein B is a boron atom.
15. A catalyst system for the polymerization of olefins comprising
the product obtained by contacting: (A) at least one transition
metal organometallic compound, and (B) an organometallic compound
obtained by contacting: a) a compound having the following formula
(I): ##STR00033## wherein R.sup.a is a linear or branched,
saturated or unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6 C.sub.20
aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7 C.sub.20 alkylaryl
group, optionally containing O, S, N, P, Si or halogen atoms; or
R.sup.a can join R.sup.d to form a C.sub.4 C.sub.7 ring; R.sup.b,
R.sup.c and R.sup.d, equal to or different from each other, are
hydrogen atoms, halogen atoms, linear or branched, saturated or
unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7
C.sub.20 arylalkyl or C.sub.7 C.sub.20 alkylaryl groups, optionally
containing O, S, N, P, Si or halogen atoms, or two or more adjacent
substituents R.sup.b, R.sup.c, and R.sup.d form one or more C.sub.4
C.sub.7 rings, optionally containing O, S, N, P or Si atoms, that
can bear substituents; b) a Lewis acid of formula (II):
MtR.sup.1.sub.3 (II) wherein Mt is a metal belonging to Group 13 of
the Periodic Table of the Elements, R.sup.1, equal to or different
from each other, are halogen atoms, halogenated C.sub.6 C.sub.20
aryl or halogenated C.sub.7 C.sub.20 alkylaryl groups; two R.sup.1
groups can also form with the metal Mt one condensed ring; and c)
optionally a compound of formula KR.sup.f.sub.3 wherein K is a
nitrogen (N) or phosphorous (P) atom; R.sup.f, equal to or
different from each other, are linear or branched, saturated or
unsaturated, C.sub.1 C.sub.30 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7
C.sub.20 arylalkyl or C.sub.7 C.sub.20 alkylaryl groups, optionally
containing O, S, N, P, Si or halogen atoms, or two R.sup.f can form
one C.sub.4 C.sub.7 ring, optionally containing O, S, N, P or Si
atoms, that can bear substituents.
16. The catalyst system according to claim 15 further comprising an
alkylating agent.
17. The catalyst system according to claim 15 wherein the
organometallic compound B) is chosen from the following formulae
(III), (V), (IV), (VI), (VII), (IX), (VIII) or (X): ##STR00034##
wherein Mt is a metal belonging to Group 13 of the Periodic Table
of the Elements (IUPAC); R.sup.1, equal to or different from each
other, are halogen atoms, halogenated C.sub.6 C.sub.20 aryl or
halogenated C.sub.7 C.sub.20 alkylaryl groups; or two R.sup.1
groups can form with the metal Mt one condensed ring; the
substituents R.sup.5, R.sup.4 and R.sup.3 equal to or different
from each other, are hydrogen atoms, halogen atoms, linear or
branched, saturated or unsaturated C.sub.1 C.sub.10 alkyl, C.sub.6
C.sub.20 aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7 C.sub.20
alkylaryl groups, optionally containing O, S, N, P, Si or halogen
atoms, or two or more adjacent substituents R.sup.3, R.sup.4 and
R.sup.5 form one or more C.sub.4 C.sub.7 rings, optionally
containing O, S, N, P or Si; R.sup.2 is a linear or branched,
saturated or unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6 C.sub.20
aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7 C.sub.20 alkylaryl
group, optionally containing O, S, N, P, Si or halogen atoms or
R.sup.2 can join R.sup.5 to form a C.sub.4 C.sub.7 ring;
##STR00035## wherein B is a boron atom; the substituents R.sup.6,
the same or different from each other, are hydrogen atoms, halogen
atoms, linear or branched, saturated or unsaturated, C.sub.1
C.sub.10 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7 C.sub.20 arylalkyl
or C.sub.7 C.sub.20 alkylaryl groups optionally containing O, S, N,
P, Si or halogen atoms, or two or more adjacent substituents
R.sup.6 form one or more C.sub.4 C.sub.7, optionally containing O,
S, N, P or Si atoms rings that can bear substituents; ##STR00036##
wherein the substituents R.sup.3', R.sup.4' and R.sup.5', equal to
or different from each other, are hydrogen atoms, halogen atoms,
linear or branched, saturated or unsaturated, C.sub.1 C.sub.10
alkyl, C.sub.6 C.sub.20 aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7
C.sub.20 alkylaryl groups, optionally containing O, S, N, P, Si or
halogen atoms, or two or more adjacent substituents R.sup.3',
R.sup.4' and R.sup.5' form one or more C.sub.4 C.sub.7 rings,
optionally containing O, S, N, P or Si atoms, that can bear
substituents; said rings can be aliphatic and optionally contain
double bonds; with the proviso that said rings are not aromatic;
R.sup.2' is a linear or branched, saturated or unsaturated, C.sub.1
C.sub.10 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7 C.sub.20 arylalkyl
or C.sub.7 C.sub.20 alkylaryl group, optionally containing O, S, N,
P, Si or halogen atoms; or R.sup.2' can join R.sup.5' to form a
C.sub.4 C.sub.7 ring; ##STR00037## wherein K is a nitrogen (N) or
phosphorous (P) atom; R.sup.f, equal to or different from each
other, are linear or branched, saturated or unsaturated, C.sub.1
C.sub.30 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7 C.sub.20 arylalkyl
or C.sub.7 C.sub.20 alkylaryl groups, optionally containing O, S,
N, P, Si or halogen atoms, or two R.sup.f can form one C.sub.4
C.sub.7 ring, optionally containing O, S, N, P or Si atoms, that
can bear substituents; ##STR00038##
18. The catalyst system according to claim 15 wherein the
transition metal organometallic compound is a metallocene compounds
belonging to the following formula (XI):
(Cp)(ZR.sup.7.sub.m).sub.n(A).sub.rML.sub.p (XI) wherein
(ZR.sup.7.sub.m).sub.n is a divalent group bridging Cp and A; Z
being C, Si, Ge, N or P, and the R.sup.7 groups, equal to or
different from each other, being hydrogen or linear or branched,
saturated or unsaturated C.sub.1 C.sub.20 alkyl, C.sub.3 C.sub.20
cycloalkyl, C.sub.6 C.sub.20 aryl, C.sub.7 C.sub.20 alkylaryl or
C.sub.7 C.sub.20 arylalkyl groups or two R.sup.7 can form a
aliphatic or aromatic C.sub.4 C.sub.7 ring; Cp is a substituted or
unsubstituted cyclopentadienyl group, optionally condensed to one
or more substituted or unsubstituted, saturated, unsaturated or
aromatic rings, containing from 4 to 6 carbon atoms, and optionally
containing at least one heteroatom; A is O, S, NR.sup.8, or
PR.sup.8 wherein R.sup.8 is hydrogen, a linear or branched,
saturated or unsaturated C.sub.1 C.sub.20 alkyl, C.sub.3 C.sub.20
cycloalkyl, C.sub.6 C.sub.20 aryl, C.sub.7 C.sub.20 alkylaryl or
C.sub.7 C.sub.20 arylalkyl, or A has the same meaning of Cp; M is a
transition metal belonging to group 4, 5 or to the lanthanide or
actinide groups of the Periodic Table of the Elements; the
substituents L, equal to or different from each other, are
monoanionic sigma ligands selected from the group consisting of
hydrogen atoms, halogen atoms, R.sup.9, OR.sup.9, OCOR.sup.9,
SR.sup.9, NR.sup.9.sub.2 and PR.sup.9.sub.2, wherein R.sup.9 is a
linear or branched, saturated or unsaturated C.sub.1 C.sub.20
alkyl, C.sub.3 C.sub.20 cycloalkyl, C.sub.6 C.sub.20 aryl, C.sub.7
C.sub.20 alkylaryl or C.sub.7 C.sub.20 arylalkyl group, optionally
containing one or more Si or Ge atoms; m is 1 when Z is N or P, and
it is 2 when Z is C, Si or Ge; n is an integer ranging from 0 to 4;
r is 0, 1 or 2; n is 0 when r is 0; p is an integer equal to the
oxidation state of the metal M minus r+1.
19. The catalyst system according to claim 15 wherein the
transition metal organometallic compound is a late transition metal
complex of formula (XII) or (XIII): L.sup.aM.sup.aX.sup.ap.sup.a
(XII) L.sup.aM.sup.aA.sup.a (XIII) wherein M.sup.a is a metal
belonging to Group 8, 9, 10 or 11 of the Periodic Table of the
Elements; L.sup.a is a bidentate or tridentate ligand of formula
(XIV): ##STR00039## wherein: Q is a C.sub.1 C.sub.50 bridging group
linking E.sup.1 and E.sup.2, optionally containing at least one
atom belonging to Groups 13 17 of the Periodic Table; E.sup.1 and
E.sup.2, equal to the same or different from each other, are
elements belonging to Group 15 or 16 of the Periodic Table and are
bonded to said metal M.sup.a; the substituents R.sup.a1, equal to
or different from each other, are selected from the group
consisting of hydrogen, linear or branched, saturated or
unsaturated C.sub.1 C.sub.20 alkyl, C.sub.3 C.sub.20 cycloalkyl,
C.sub.6 C.sub.20 aryl, C.sub.7 C.sub.20 alkylaryl and C.sub.7
C.sub.20 arylalkyl radicals, optionally containing at least one
atom belonging to groups 13 17 of the Periodic Table of the
Elements; or two R.sup.a1 substituents attached to the same atom
E.sup.1 or E.sup.2 form a saturated, unsaturated or aromatic
C.sub.4 C.sub.7 ring, having from 4 to 20 carbon atoms; m.sup.a and
n.sup.a are independently 0, 1 or 2, depending on the valence of
E.sup.1 and E.sup.2, so to satisfy the valence number of E.sup.1
and E.sup.2; q.sup.a is the charge of the bidentate or tridentate
ligand so that the oxidation state of
M.sup.aX.sup.a.sub.pX.sup.a'.sub.s or M.sup.aA.sup.a is satisfied,
and the compound (XII) or (XIII) is overall neutral; X.sup.a, equal
to or different from each other, are monoanionic sigma ligands
selected from the group consisting of hydrogen, halogen, R.sup.a,
OR.sup.a, OSO.sub.2CF.sub.3, OCOR.sup.a, SR.sup.a, --NR.sup.a.sub.2
and PR.sup.a.sub.2 groups, wherein the R.sup.a substituents are
linear or branched, saturated or unsaturated, C.sub.1 C.sub.20
alkyl, C.sub.3 C.sub.20 cycloalkyl, C.sub.6 C.sub.20 aryl, C.sub.7
C.sub.20 alkylaryl or C.sub.7 C.sub.20 arylalkyl radicals,
optionally containing one or more atoms belonging to groups 13 17
of the Periodic Table of the Elements; or two X.sup.a groups form a
metallacycle ring containing from 3 to 20 carbon atoms; p.sup.a is
an integer ranging from 0 to 3, so that the final compound (XII) or
(XIII) is overall neutral; and A.sup.a is a .pi.-allyl or a
.pi.-benzyl group.
20. A process for the polymerization of at least one olefin
comprising contacting at least one olefin under polymerization
conditions with a catalyst system, comprising the product obtained
by contacting: (A) at least one transition metal organometallic
compound; and (B) an organometallic compound obtained by
contacting: a) a compound having the following formula (I):
##STR00040## wherein R.sup.a is a linear or branched, saturated or
unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7
C.sub.20 arylalkyl or C.sub.7 C.sub.20 alkylaryl group, optionally
containing O, S, N, P, Si or halogen atoms; or R.sup.a can join
R.sup.d to form a C.sub.4 C.sub.7 ring; R.sup.b, R.sup.c and
R.sup.d, equal to or different from each other, are hydrogen atoms,
halogen atoms, linear or branched, saturated or unsaturated,
C.sub.1 C.sub.10 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7 C.sub.20
arylalkyl or C.sub.7 C.sub.20 alkylaryl groups, optionally
containing O, S, N, P, Si or halogen atoms, or two or more adjacent
substituents R.sup.b, R.sup.c, and R.sup.d form one or more C.sub.4
C.sub.7 rings, optionally containing O, S, N, P or Si atoms, that
can bear substituents; b) a Lewis acid of formula (II):
MtR.sup.1.sub.3 (II) wherein Mt is a metal belonging to Group 13 of
the Periodic Table of the Elements; R.sup.1, equal to or different
from each other, are halogen atoms, halogenated C.sub.6 C.sub.20
aryl or halogenated C.sub.7 C.sub.20 alkylaryl groups; two R.sup.1
groups can also form with the metal Mt one condensed ring; and c)
optionally a compound of formula KR.sup.f.sub.3 wherein K is a
nitrogen (N) or phosphorous (P) atom; R.sup.f, equal to or
different from each other, are linear or branched, saturated or
unsaturated, C.sub.1 C.sub.30 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7
C.sub.20 arylalkyl or C.sub.7 C.sub.20 alkylaryl groups, optionally
containing O, S, N, P, Si or halogen atoms, or two R.sup.f can form
one C.sub.4 C.sub.7 ring, optionally containing O, S, N, P or Si
atoms, that can bear substituents.
Description
The present invention relates to organometallic compounds, to
catalyst systems for the polymerization of olefins comprising such
organometallic compounds and to a process for the polymerization of
olefins carried out in the presence of the above catalyst system.
Homogeneous catalytic systems based on metallocene complexes are
known to be active in the polymerization of olefins; said complexes
must be activated by means of suitable cocatalytic compounds.
The first generation of cocatalysts developed for homogeneous
metallocene olefin polymerization consisted of alkyl aluminum
chlorides (AlR.sub.2Cl), wherein substituents R are preferably
methyl or ethyl; these cocatalysts exhibit low ethylene
polymerization activity levels and negligible propylene
polymerization activity.
The second generation of cocatalysts comprised the class of
alkylalumoxanes, commonly obtained by reacting trialkyl aluminum
compound and water in a molar ratio of 1:1 to 100:1; these
alumoxanes are oligomeric linear and/or cyclic compounds
represented by the formulae:
##STR00002## for linear oligomeric alumoxanes, and
##STR00003## for cyclic oligomeric alumoxanes, wherein the
substituents R are usually methyl, ethyl or isobutyl groups, n
ranges from 0 to 40, and m ranges from 3 to 40. Methylalumoxane
(MAO) is the most widely used cocatalyst.
Nevertheless alkylalumoxanes, and in particular methylalumoxane,
though very active in metallocene-based catalyst systems, exhibit
several inherent problems in use, such as the need for high
alumoxane/metallocene molar ratios to produce satisfactory
catalytic activities, their high reactivity toward impurities
(moisture, alcohols etc.) and their easy flammability. Moreover, it
has not been possible to isolate characterizable metallocene active
species using MAO. Accordingly, some of the developments in this
area involved a search for alternative cocatalysts.
B(C.sub.6F.sub.5).sub.4.sup.- types of non-coordinating anions have
been developed as cocatalysts for metallocene-based systems. More
specifically, these activators are ion-exchange compounds
comprising a trialkyl or dialkylammonium cation, which will
irreversibly react with a metallocene, and a fluorinated arylborate
anion, capable of stabilizing the metallocene cation complex and
sufficiently labile to permit displacement by ethylene during
polymerization (see for instance WO 91/02012). In particular, they
have the advantage of being used in a 1:1 catalyst-cocatalyst
ratio. Therefore, it is usually not necessary to remove the small
amount of boron from the final polymer, unlike the aluminum-based
cocatalysts mentioned above. As preferred activators are
tri(n-butyl)ammonium tetrakis(pentafluorophenyl)boron and
N,N-dimethylanilinium tetrakis(pentafluorophenyl)boron.
These cocatalysts exhibit high activities but, from a synthetic
point of view, the industrial production of these cocatalysts is
quite expensive.
Finally, these B(C.sub.6F.sub.5).sub.4.sup.- anions are generally
used in the form of the corresponding ammonium salts, thus leading
to the release of aminic by-products in consequence of the
metallocene activation. In addition they have low solubility in
polymerization solvents The fourth generation of cocatalysts is
B(C.sub.6F.sub.5).sub.3. The anion MeB(C.sub.6F.sub.5).sub.3.sup.-
formed after Me.sup.- abstraction from the metallocene dimethyl
complex is weakly coordinated to the electrondeficient metal
center, thus resulting in a decrease of the catalytic activity and
in addition the catalyst system is not stable.
An alternative route for using B(C.sub.6F.sub.5).sub.3 has been
proposed by B. Temme in Journal of Organometallic Chemistry, 488
(1995), 177 182. Biscyclopentadienyl-methyl-pyrrolidyl zirconocene
has been treated with B(C.sub.6F.sub.5).sub.3 with the formation of
the pyrrolydyl borate and the metallocene cation. In this paper it
is reported that the obtained salt is catalytically active and
polymerizes ethylene even if with a moderate activity.
WO 99/64476 describes a process for the preparation of polyolefins
by using a catalyst system comprising a metallocene compound, a
Lewis acid-base complex and a tri-n-alkylaluminum compound. As
described at page 4 and illustrated in the figures, the function of
the Lewis base is to inhibit the reaction between the metallocene
compounds and the Lewis acid. Only upon addition of the
tri-n-alkylaluminum compound the catalyst system becomes active.
This catalyst system does not solve completely the problems of the
use B(C.sub.6F.sub.5).sub.3, for the reason that the anion that is
weakly coordinated to the electrondeficient metal center is always
of the type MeB(C.sub.6F.sub.5).sub.3.sup.- and therefore the
active catalyst system is not stable for a long time.
The recently published WO 01/62764 describes a new class of
cocatalysts obtainable by contacting a N--H pyrrole derivative with
a Lewis acid. The catalyst system comprising these cocatalyts and a
metallocene compound can be isolated and identified.
Thus there is still the need to find a new cocatalyst which reduces
the use of excess of cocatalyst with respect to alkylaluminoxanes,
does not lead to the release of undesired by-products after the
metallocene activation, and provides stable catalytic
compositions.
The present invention concerns an organometallic compound
obtainable by contacting: a) a compound having the following
formula (I):
##STR00004## wherein: R.sup.a is a linear or branched, saturated or
unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7
C.sub.20 arylalkyl or C.sub.7 C.sub.20 alkylaryl group, optionally
containing O, S, N, P, Si or halogen atoms; or R.sup.a can join
R.sup.d to form a C.sub.4 C.sub.7 ring; preferably R.sup.a is a
C.sub.1 C.sub.10 alkyl, or C.sub.6 C.sub.20 aryl group; more
preferably R.sup.a is methyl, ethyl, propyl, phenyl or a naphtyl
group. R.sup.b, R.sup.c and R.sup.d, equal to or different from
each other, are hydrogen atoms, halogen atoms, linear or branched,
saturated or unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6 C.sub.20
aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7 C.sub.20 alkylaryl
groups, optionally containing O, S, N, P, Si or halogen atoms, or
two or more adjacent substituents R.sup.b, R.sup.c, and R.sup.d
form one or more C.sub.4 C.sub.7 rings, optionally containing O, S,
N, P or Si atoms, that can bear substituents; with b) a Lewis acid
of formula (I) MtR.sup.1.sub.3 (II) wherein Mt is a metal belonging
to Group 13 of the Periodic Table of the Elements (IUPAC); R.sup.1,
equal to or different from each other, are halogen atoms,
halogenated C.sub.6 C.sub.20 aryl and halogenated C.sub.7 C.sub.20
alkylaryl groups; two R.sup.1 groups can also form with the metal
Mt one condensed ring, such as for example 9-borafluorene
compounds.
Preferably Mt is B or Al, and more preferably is B; the
substituents R.sup.1 are C.sub.6F.sub.5, C.sub.6F.sub.4H,
C.sub.6F.sub.3H.sub.2, C.sub.6H.sub.3(CF.sub.3).sub.2,
perfluoro-biphenyl, heptafluoro-naphthyl, hexafluoro-naphthyl and
pentafluoro-naphthyl; most preferred R.sup.1 substituents are
C.sub.6F.sub.5 radicals.
Preferred organometallic compounds are those belonging to the
following two classes (1) and (2), having respectively formula
(III) and (IV).
Class (1)
Organometallic compounds belonging to class (1) have the following
formula (III)
##STR00005## wherein Mt is a metal belonging to Group 13 of the
Periodic Table of the Elements (IUPAC); R.sup.1, equal to or
different from each other, are halogen atoms, halogenated C.sub.6
C.sub.20 aryl or halogenated C.sub.7 C.sub.20 alkylaryl groups; or
two R.sup.1 groups can form with the metal Mt one condensed ring,
such as for example 9-borafluorene compounds; the substituents
R.sup.5, R.sup.4 and R.sup.3 equal to or different from each other,
are hydrogen atoms, halogen atoms, linear or branched, saturated or
unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7
C.sub.20 arylalkyl or C.sub.7 C.sub.20 alkylaryl groups, optionally
containing O, S, N, P, Si or halogen atoms, or two or more adjacent
substituents R.sup.3, R.sup.4 and R.sup.5 form one or more C.sub.4
C.sub.7 rings, optionally containing O, S, N, P or Si; preferably
R.sup.4 and R.sup.5 form one condensed C.sub.5 C.sub.6 aromatic
ring, optionally containing O, S, N, or P atoms, that replace one
or more carbons of the aromatic ring and can bear substituents;
preferably R.sup.3 is hydrogen; R.sup.2 is a linear or branched,
saturated or unsaturated, C.sub.1 C.sub.10 allyl, C.sub.6 C.sub.20
aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7 C.sub.20 alkylaryl
group, optionally containing O, S, N, P, Si or halogen atoms or
R.sup.2 can join R.sup.5 to form a C.sub.4 C.sub.7 ring; preferably
R.sup.2 is a C.sub.1 C.sub.10 alkyl, or C.sub.6 C.sub.20 aryl
group; more preferably R.sup.2 is methyl, ethyl, propyl, phenyl or
a naphtyl group.
Preferably in the organometallic compounds of formula (III) Mt is B
or Al, and more preferably is B; the substituents R.sup.1 equal to
or different from each other, C.sub.6F.sub.5, C.sub.6F.sub.4H,
C.sub.6F.sub.3H.sub.2, C.sub.6H.sub.3(CF.sub.3).sub.2,
perfluoro-biphenyl, heptafluoro-naphthyl, hexafluoro-naphthyl and
pentafluoro-naphthyl; even more preferably, R.sup.1 is
C.sub.6F.sub.5.
A preferred subclass of organometallic compounds of formula (III)
is that of formula (V):
##STR00006## wherein B is a boron atom; the substituents R.sup.1,
R.sup.2 and R.sup.3 have the meaning reported above and the
substituents R.sup.6, the same or different from each other, are
hydrogen atoms, halogen atoms, linear or branched, saturated or
unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7
C.sub.20 arylalkyl or C.sub.7 C.sub.20 alkylaryl groups optionally
containing O, S, N, P, Si or halogen atoms, or two or more adjacent
substituents R.sup.6 form one or more C.sub.4 C.sub.7 rings,
optionally containing O, S, N, P or Si atoms that can bear
substituents; preferably, R.sup.6 are selected from the group
consisting of hydrogen atoms, halogen atoms, and linear or
branched, saturated or unsaturated C.sub.1 C.sub.10 alkyl. Class
(2)
Organometallic compounds belonging to class (2) have the following
formula (IV):
##STR00007## wherein Mt and R.sup.1 are defined as above; the
substituents R.sup.3', R.sup.4' and R.sup.5' equal to or different
from each other, are hydrogen atoms, halogen atoms, linear or
branched, saturated or unsaturated, C.sub.1 C.sub.10 alkyl, C.sub.6
C.sub.20 aryl, C.sub.7 C.sub.20 arylalkyl or C.sub.7 C.sub.20
alkylaryl groups, optionally containing O, S, N, P, Si or halogen
atoms, or two or more adjacent substituents R.sup.3', R.sup.4' and
R.sup.5' form one or more C.sub.4 C.sub.7 rings optionally
containing O, S, N, P or Si atoms, that can bear substituents; said
rings can be aliphatic or optionally can contain double bonds;
R.sup.2' is a linear or branched, saturated or unsaturated, C.sub.1
C.sub.10 alkyl, C.sub.6 C.sub.20 aryl, C.sub.7 C.sub.20 arylalkyl
or C.sub.7 C.sub.20 alkylaryl group, optionally containing O, S, N,
P, Si or halogen atoms; or R.sup.2' can join R.sup.5' to form a
C.sub.4 C.sub.7 ring; preferably R.sup.2' is a C.sub.1 C.sub.10
alkyl, or C.sub.6 C.sub.20 aryl group; more preferably R.sup.2' is
methyl, ethyl, propyl, tertbutyl, phenyl or a naphtyl group.
Preferably the substituents R.sup.3', R.sup.4' and R.sup.5', are
hydrogen atoms, linear or branched, saturated or unsaturated,
C.sub.1 C.sub.10 alkyl, optionally containing O, S, N, P, Si or
halogen atoms, or two or more adjacent substituents R.sup.3',
R.sup.4' and R.sup.5' form one or more C.sub.4 C.sub.7 rings
optionally containing O, S, N, P or Si atoms, that can bear
substituents; said rings can be aliphatic or optionally can
contains double bonds, with the proviso that said rings are not
aromatic.
A preferred subclass of organometallic compounds of formula (IV) is
that of formula (VI):
##STR00008## wherein the substituents R.sup.1 and R.sup.2' have the
meaning described above and the substituent R.sup.5' is a C.sub.1
C.sub.10 alkyl group; preferably R.sup.5' is a methyl or ethyl
group.
The organometallic compounds of the invention are easily prepared
by reacting, in about stoichiometric amounts, a compound having the
formula (I):
##STR00009## wherein R.sup.a, R.sup.b, R.sup.c R.sup.d and R.sup.e
are described above; with a Lewis acid of formula (II)
MtR.sup.1.sub.3 (II) wherein Mt and R.sup.1 are described
above.
The reaction between said Lewis acid and the compound of formula
(I) is preferably carried out in an aprotic solvent, even more
preferably in a polar aprotic solvent (such as toluene, diethyl
ether or CH.sub.2Cl.sub.2), at room temperature, the reaction can
be carried out also in the presence of a small amount of water,
preferably less than one molar equivalent with respect to the Lewis
acid.
A further object of the present invention is a salt obtainable by
contacting, in any order: a) a compound having formula (I) as
described above; b) a Lewis acid of formula (II) as described
above; and c) a compound of formula KR.sup.f.sub.3 wherein K is a
nitrogen (N) or phosphorous (P) atom; preferably K is nitrogen;
R.sup.f, equal to or different from each other, are linear or
branched, saturated or unsaturated, C.sub.1 C.sub.30 alkyl, C.sub.6
C.sub.20 aryl, C.sub.7 C.sub.20 arylalkyl and C.sub.7 C.sub.20
alkylaryl groups, optionally containing O, S, N, P, Si or halogen
atoms, or two R.sup.f can form one C.sub.4 C.sub.7 ring, optionally
containing O, S, N, P or Si atoms, that can bear substituents;
preferably R.sup.f is selected from the group consisting of linear
or branched, saturated or unsaturated, C.sub.1 C.sub.30 alkyl.
This salt can be used as cocatalyst for the polymerization of
olefins.
Preferred salts compounds are those belonging to the following two
classes (3) and (4), having respectively formulas (VII) and
(VIII).
Class (3)
Salts belonging to class (3) have formula (VI):
##STR00010## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
Mt, K and R.sup.f have the meaning described above.
A preferred subclass of salts of formula (VII) is that of formula
(IX):
##STR00011## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.6, B, K and
R.sup.f have the meaning described above. Class (4)
Salts belonging to class (4) have formula (VIII):
##STR00012## wherein R.sup.1, R.sup.2', R.sup.3', R.sup.4',
R.sup.5', Mt, K and R.sup.f have the meaning described above.
A preferred subclass of salts of formula (VIII) is that of formula
(X):
##STR00013## wherein R.sup.1, R.sup.2', R.sup.5', Mt, K and R.sup.f
have the meaning described above.
A process for preparing the above described salts comprises the
following steps: a) contacting at least one equivalent of a
compound of formula (I) with one equivalent of a Lewis acid of
formula (II), wherein the compound of formula (I) and (II) has been
described above; and b) optionally isolating the reaction product
of step a) and then adding at least one equivalent of a compound of
formula KR.sup.f.sub.3, wherein K and R.sup.f have been described
above.
The two steps described above can be carried out both by isolating
the intermediate product formed in step a), generally by filtration
or evaporation of the solvent, or carried out "one pot" without
isolating the intermediate product; preferably the reaction is
carried out in an aprotic solvent, even more preferably in a polar
aprotic solvent (such as toluene, diethyl ether or
CH.sub.2Cl.sub.2), at room temperature. The reaction can be carried
out also in the presence of little amount of water, preferably
equal to or less than one molar equivalent with respect to the
Lewis acid. The final product is generally isolated by filtration
or evaporation of the solvent. An alternative process for preparing
the above described salts comprises the step of contacting a
compound of formula (III), (IV), (V) or (VI) with at least one
equivalent of a compound of formula KR.sup.f.sub.3, wherein K and
R.sup.f have been described above.
Non limitative examples of compounds belonging to formula (I) are:
N-methyl-pyrrole; N-methyl-2-ethylpyrrole;
N-methyl-2,4-dimethylpyrrole; N-methyl-4,5,6,7-tetrahydroindole;
N-methyl-2,4-dimethyl-3-ethylpyrrole; N-methyl-indole;
N-methyl-3-methylindole; N-methyl-4-methylindole;
N-methyl-5-methylindole; N-methyl-6-methylindole;
N-methyl-7-methylindole; N-methyl-5-fluoroindole;
N-methyl-4-chloroindole; N-methyl-5-chloroindole;
N-methyl-6-chloroindole; N-methyl-5-bromoindole;
N-methyl-5-methoxyindole; N-methyl-4-methoxyindole;
N-methyl-5,6-dimethoxyindole; N-methyl-5-benzyloxyindole; and the
corresponding N-ethyl, N-propyl, N-phenyl and N-naphtyl
compounds.
Example of Lewis acid of formula (II) are:
tris(pentafluorophenyl)borane; tris(heptafluoronaphthyl)borane;
tris(2,3,5,6,7,8-hexafluoronaphthyl)borane;
tris(2,4,5,6,7,8-hexafluoronaphthyl)borane;
tris(3,4,5,6,7,8-hexafluoronaphthyl)borane;
tris(2,3,4,6,7,8-hexafluoronaphthyl)borane;
tris(2,3,4,5,7,8-hexafluoronaphthyl)borane;
tris(2,3,5,6,7,8-hexafluoro-4-methylnaphthyl)borane;
tris(2,4,5,6,7,8-hexafluoro-3-methylnaphthyl)borane;
tris(3,4,5,6,7,8-hexafluoro-2-methylnaphthyl)borane;
tris(2,3,4,6,7,8-hexafluoro-5-methylnaphthyl)borane;
tris(2,3,4,5,7,8-hexafluoro-6-methylnaphthyl)borane;
tris(nonafluorobiphenyl)borane;
tris(2,2',3,3',5,5',6,6'-octafluorobiphenyl)borane;
tris(3,3',4,4',5,5',6,6'-octafluorobiphenyl)borane;
tris(2,2',4,4',5,5',6,6'-octafluorobiphenyl)borane;
tris(2,2',3,3',4,4',6,6'-octafluorobiphenyl)borane;
tris(2,2',3,3',4,4',5,5'-octafluorobiphenyl)borane;
tris(2,2',3,3',5,5',6,6'-octafluorobiphenyl)borane;
tris(3,3',4,4',5,5',6,6'-octafluorobiphenyl)borane;
tris(2,2',4,4',5,5',6,6'-octafluorobiphenyl)borane;
tris(2,2',3,3',4,4',6,6'-octafluoro-5,5'-methylbiphenyl)borane;
tris(2,2',3,3',4,4',5,5'-octafluoro-6,6'-methylbiphenyl)borane;
tris(2,2',3,3',5,5',6,6'-octafluoro-4,4'-biphenyl)borane;
tris(3,3',4,4',5,5',6,6'-octafluoro-2,2'-biphenyl)borane;
tris(2,2',4,4',5,5',6,6'-octafluoro-3,3'-biphenyl)borane;
tris(2,3,4,6-tetrafluorophenyl)borane;
tris(2,3,5,6-tetrafluorophenyl)borane;
tris(2,3,5-trifluorophenyl)borane,
tris(2,3,6-trifluorophenyl)borane; tris(1,3-difluorophenyl)borane,
tris(2,3,5,6-tetrafluoro-4-methylphenyl)borane;
tris(2,3,4,6-tetrafluoro-5-methylphenyl)borane;
tris(2,6-difluoro-3-methylphenyl)borane;
tris(2,4-difluoro-5-methylphenyl)borane;
tris(3,5-difluoro-2-methylphenyl)borane;
fluorobis(pentafluorophenyl)borane;
chlorobis(pentafluorophenyl)borane;
dichloro(pentafluorophenyl)borane; difluoro
(pentafluorophenyl)borane; 9-chloro-9-boroperfluorofluorene;
9-methyl-9-boroperfluorpfluorene;
9-pentafluorophenyl-9-boroperfluorofluorene and
9-bromo-9-boroperfluorofluorene.
It is another object of the present invention a catalyst system for
the polymerization of olefins comprising the product obtained by
contacting: (A) at least one transition metal organometallic
compound, and, (B) an organometallic compound obtainable by
contacting a) a compound having the following formula (I):
##STR00014## wherein R.sup.a, R.sup.b, R.sup.c and R.sup.d have the
meaning described above b) a Lewis acid of formula (II)
MtR.sup.1.sub.3 (II); wherein Mt and R.sup.1 have the meaning
described above; and c) optionally a compound of formula
KR.sup.f.sub.3, wherein K and R.sup.f have the meaning described
above.
The catalyst system can optionally further comprise an alkylating
agent.
Preferably the catalyst system of the present invention of olefins
comprises the product obtained by contacting: (A) at least one
transition metal organometallic compound; (B) an organometallic
compound belonging to class (1) (compounds of formula (III), or
(V)) or class (2) (compounds of formula (IV) or (VI)) as described
above or a salt belonging to class (3) (salts of formula (VII) or
(IX)) or class (4) (salts of formula (VIII) or (X)).
The catalyst system can optionally further comprise an alkylating
agent.
Transition metal organometallic compounds for use in the catalyst
system in accordance with the present invention are compounds
suitable as olefin polymerization catalysts by coordination or
insertion polymerization. The class includes known transition metal
compounds useful in traditional Ziegler-Natta coordination
polymerization, metallocene compounds and the transition metal
compounds known to be useful in coordination polymerization. These
typically include Group 4 10 transition metal compounds wherein at
least one metal ligand can be abstracted by the catalyst
activators. As a rule, when said ligand is hydrogen or an
hydrocarbyl group containing from 1 to 20 carbon atoms optionally
containing silicon atoms, the transition metal organometallic
catalyst compounds can be used as such, otherwise an alkylating
agent has to be used in order to alkylate said catalyst. The
alkylation can be carried out in a separate step or in situ.
The alkylating agent is a compound able to react with the
transition metal organometallic catalyst compounds and exchange
said ligand that can be abstracted, with an alkyl group. Preferably
said alkylating agent is selected from the group consisting of
R.sup.10Li, R.sup.10Na, R.sup.10K, R.sup.10MgU or
AlR.sup.10.sub.3-zW.sub.z, or alumoxanes, wherein R.sup.10 can be
C.sub.1 C.sub.10 alkyl, alkenyl or alkylaryl radicals, optionally
containing one or more Si or Ge atoms, z is 0, 1 or 2 or a non
integer number ranging from 0 to 2; U is chlorine, bromine or
iodine and W is hydrogen, chlorine, bromine or iodine atom;
non-limiting examples of R.sup.10 are methyl, ethyl, butyl and
benzyl; non limiting example of AlR.sup.10.sub.3-zW.sub.z,
compounds are trimethylaluminum (TMA),
tris(2,4,4-trimethyl-pentyl)aluminum (TIOA),
tris(2-methyl-propyl)aluminum (TIBA),
tris(2,3,3-trimethyl-butyl)aluminum,
tris(2,3-dimethyl-hexyl)aluminum, tris(2,3-dimethyl-butyl)aluminum,
tris(2,3-dimethyl-pentyl)aluminum,
tris(2,3-dimethyl-heptyl)aluminum,
tris(2-methyl-3-ethyl-pentyl)aluminum and
tris(2-ethyl-3,3-dimethylbutyl). Non limiting example of alumoxanes
are: methylalumoxane (MAO), tetra-(isobutyl)alumoxane (TIBAO),
tetra-(2,4,4-trimethyl-pentyl)alumoxane (TIOAO),
tetra-(2,3-dimethylbutyl)alumoxane (TDMBAO) and
tetra-(2,3,3-trimethylbutyl)alumoxane (TTMBAO).
Different from the catalyst system disclosed in WO 99/64476, the
catalyst system of the present invention is stable and can be
isolated.
A preferred class of transition metal organometallic compounds are
metallocene compounds belonging to the following formula (XI)
(Cp)(ZR.sup.7.sub.m).sub.n(A).sub.rML.sub.p (XI) wherein
(ZR.sup.7.sub.m).sub.n is a divalent group bridging Cp and A; Z
being C, Si, Ge, N or P, and the R.sup.7 groups, equal to or
different from each other, being hydrogen or linear or branched,
saturated or unsaturated C.sub.1 C.sub.20 alkyl, C.sub.3 C.sub.20
cycloalkyl, C.sub.6 C.sub.20 aryl, C.sub.7 C.sub.20 alkylaryl or
C.sub.7 C.sub.20 arylalkyl groups or two R.sup.7 can form a
aliphatic or aromatic C.sub.4 C.sub.7 ring; Cp is a substituted or
unsubstituted cyclopentadienyl group, optionally condensed to one
or more substituted or unsubstituted, saturated, unsaturated or
aromatic rings, containing from 4 to 6 carbon atoms, optionally
containing one or more heteroatoms;
A is O, S, NR.sup.8, PR.sup.8 wherein R.sup.8 is hydrogen, a linear
or branched, saturated or unsaturated C.sub.1 C.sub.20 alkyl,
C.sub.3 C.sub.20 cycloalkyl, C.sub.6 C.sub.20 aryl, C.sub.7
C.sub.20 alkylaryl or C.sub.7 C.sub.20 arylalkyl, or A has the same
meaning of Cp; M is a transition metal belonging to group 4, 5 or
to the lanthanide or actinide groups of the Periodic Table of the
Elements IUPAC version); the substituents L, equal to or different
from each other, are monoanionic sigma ligands selected from the
group consisting of hydrogen, halogen, R.sup.9, OR.sup.9,
OCOR.sup.9, SR.sup.9, NR.sup.9.sub.2 and PR.sup.9.sub.2, wherein
R.sup.9 is a linear or branched, saturated or unsaturated C.sub.1
C.sub.20 alkyl, C.sub.3 C.sub.20 cycloalkyl, C.sub.6 C.sub.20 aryl,
C.sub.7 C.sub.20 alkylaryl or C.sub.7 C.sub.20 arylalkyl group,
optionally containing one or more Si or Ge atoms; preferably, the
substituents L are the same; m is 1 or 2, and more specifically it
is 1 when Z is N or P, and it is 2 when Z is C, Si or Ge; n is an
integer ranging from 0 to 4; r is 0, 1 or 2; preferably 0 or 1; n
is 0 when r is 0; p is an integer equal to the oxidation state of
the metal M minus r+1; i.e. minus 3 when r=2, minus 2 when r=1, and
minus 1 when r=0, and ranges from 1 to 4.
In the metallocene compound of formula (XI), the divalent bridge
(ZR.sup.7.sub.m).sub.n is preferably selected from the group
consisting of CR.sup.7.sub.2, (CR.sup.7.sub.2).sub.2,
(CR.sup.7.sub.2).sub.3, SiR.sup.7.sub.2, GeR.sup.7.sub.2, NR.sup.7
and PR.sup.7, R.sup.7 having the meaning reported above; more
preferably, said divalent bridge is Si(CH.sub.3).sub.2, SiPh.sub.2,
CH.sub.2, (CH.sub.2).sub.2, (CH.sub.2).sub.3 or
C(CH.sub.3).sub.2.
The variable m is preferably 1 or 2; the variable n ranges
preferably from 0 to 4 and, when n>1, the atoms Z can be the
same or different from each other, such as in divalent bridges
CH.sub.2--O, CH.sub.2--S and CH.sub.2--Si(CH.sub.3).sub.2.
The ligand Cp, which is .pi.-bonded to said metal M, is preferably
selected from the group consisting of cyclopentadienyl, mono-, di-,
tri- and tetra-methyl cyclopentadienyl;
4-.sup.tbutyl-cyclopentadienyl; 4-adamantyl-cyclopentadienyl;
indenyl; mono-, di-, tri- and tetra-methyl indenyl; 2-methyl
indenyl, 3-.sup.tbutyl-indenyl, 2-methyl-4-phenyl indenyl,
2-methyl-4,5 benzo indenyl; 3-trimethylsilyl-indenyl;
4,5,6,7-tetrahydroindenyl; fluorenyl;
5,10-dihydroindeno[1,2-b]indol-10-yl; N-methyl- or
N-phenyl-5,10-dihydroindeno [1,2-b]indol-10-yl;
5,6-dihydroindeno[2,1-b]indol-6-yl; N-methyl-or
N-phenyl-5,6-dihydroindeno[2,1-b]indol-6-yl; azapentalene-4-yl;
thiapentalene-4-yl; azapentalene-6-yl; thiapentalene-6-yl; mono-,
di- and tri-methyl-azapentalene-4-yl,
2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene.
The group A is O, S, N(.sup.8), wherein R.sup.8 is hydrogen, a
linear or branched, saturated or unsaturated C.sub.1 C.sub.20
alkyl, C.sub.3 C.sub.20 cycloalkyl, C.sub.6 C.sub.20 aryl, C.sub.7
C.sub.20 alkylaryl or C.sub.7 C.sub.20 arylalkyl, preferably
R.sup.8 is methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl,
phenyl, p-n-butyl-phenyl, benzyl, cyclohexyl and cyclododecyl; more
preferably R.sup.8 is t-butyl; or A has the same meaning of Cp.
Non limiting examples of compounds belonging to formula (XI) are
the following compounds (when possible in either their meso or
racemic isomers, or mixtures thereof):
bis(cyclopentadienyl)zirconium dimethyl; bis(indenyl)zirconium
dimethyl; bis(tetrahydroindenyl)zirconium dimethyl;
bis(fluorenyl)zirconium dimethyl;
(cyclopentadienyl)(indenyl)zirconium dimethyl;
(cyclopentadienyl)(fluorenyl)zirconium dimethyl;
(cyclopentadienyl)(tetrahydroindenyl)zirconium dimethyl;
(fluorenyl)(indenyl)zirconium dimethyl;
dimethylsilanediylbis(indenyl)zirconium dimethyl,
dimethylsilanediylbis(2-methyl-4-phenylindenyl)zirconium dimethyl,
dimethylsilanediylbis(4-naphthylindenyl)zirconium dimethyl,
dimethylsilanediylbis(2-methylindenyl)zirconium dimethyl,
dimethylsilanediylbis(2-methyl-4-t-butylindenyl)zirconium dimethyl,
dimethylsilanediylbis(2-methyl-4-isopropylindenyl)zirconium
dimethyl, dimethylsilanediylbis(2,4-dimethylindenyl)zirconium
dimethyl, dimethylsilanediylbis(2-methyl-4,5-benzoindenyl)zirconium
dimethyl, dimethylsilanediylbis(2,4,7-trimethylindenyl)zirconium
dimethyl, dimethylsilanediylbis(2,4,6-trimethylindenyl)zirconium
dimethyl, dimethylsilanediylbis(2,5,6-trimethylindenyl)zirconium
dimethyl,
methyl(phenyl)silanediylbis(2-methyl-4,6-diisopropylindenyl)-zirconium
dimethyl,
methyl(phenyl)silanediylbis(2-methyl-4-isopropylindenyl)-zircon-
ium dimethyl, 1,2-ethylenebis(indenyl)zirconium dimethyl,
1,2-ethylenebis(4,7-dimethylindenyl)zirconium dimethyl,
1,2-ethylenebis(2-methyl-4-phenylindenyl)zirconium dimethyl,
1,4-butanediylbis(2-methyl-4-phenylindenyl)zirconium dimethyl,
1,2-ethylenebis(2-methyl-4,6-diisopropylindenyl)zirconium dimethyl,
1,4-butanediylbis(2-methyl-4-isopropylindenyl)zirconium dimethyl,
1,4-butanediylbis(2-methyl-4,5-benzoindenyl)zirconium dimethyl,
1,2-ethylenebis(2-methyl-4,5-benzoindenyl)zirconium dimethyl,
[4-(.eta..sup.5-cyclopentadienyl)-4,6,6-trimethyl(.eta..sup.5-4,5-tetrahy-
dro-pentalene)]dimethylzirconium,
[4-(.eta..sup.5-3'-trimethylsilylcyclopentadienyl)-4,6,6-trimethyl(.eta..-
sup.5-4,5-tetrahydropentalene)]dimethylzirconium,
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)-1,2-ethane-di-
methyltitanium,
(methylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethylsilyl-dime-
thyltitanium,
(methylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)-1,2-ethanediyl-di-
methyltitanium,
(tertbutylamido)-(2,4-dimethyl-2,4-pentadien-1-yl)dimethylsilyl-dimethylt-
itanium, bis(1,3-dimethylcyclopentadienyl)zirconium dimethyl,
methylene(3-methyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-
-b:4,3-b']dithiophene)zirconium dimethyl;
methylene(3-isopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[-
1,2-b:4,3-b']dithiophene)zirconium dimethyl;
methylene(2,4-dimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl--
[1,2-b:4,3-b']dithiophene)zirconium dimethyl;
methylene(2,3,5-trimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadien-
yl-[1,2-b:4,3-b']dithiophene)zirconium dimethyl;
methylene-1-(indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b']dithi-
ophene)zirconium dimethyl and dimethyl;
methylene-1-(indenyl)-7-(2,5-ditrimethylsilylcyclopentadienyl-[1,2-b:4,3--
b']dithiophene)zirconium dimethyl;
methylene-1-(3-isopropyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:-
4,3-b']dithiophene)zirconium dimethyl;
methylene-1-(2-methyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-
-b']dithiophene)zirconium dimethyl;
methylene-1-(tetrahydroindenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,-
3-b']dithiophene)zirconium dimethyl;
methylene(2,4-dimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl--
[1,2-b:4,3-b']dioxazol)zirconium dimethyl;
methylene(2,3,5-trimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadien-
yl-[1,2-b:4,3-b']dioxazol)zirconium dimethyl;
methylene-1-(indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b']dioxa-
zol)zirconium dimethyl and dimethyl;
isopropylidene(3-methyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-
-[1,2-b:4,3-b']dithiophene)zirconium dimethyl;
isopropylidene(2,4-dimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadi-
enyl-[1,2-b:4,3-b']dithiophene)zirconium dimethyl;
isopropylidene(2,4-diethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadie-
nyl-[1,2-b:4,3-b']dithiophene)zirconium dimethyl;
isopropylidene(2,3,5-trimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopent-
adienyl-[1,2-b:4,3-b']dithiophene)zirconium dimethyl;
isopropylidene-1-(indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b']-
dithiophene)zirconium dimethyl;
isopropylidene-1-(2-methyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2--
b:4,3-b']dithiophene)zirconium dimethyl;
dimethylsilandiyl-1-(2-methyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1-
,2-b:4,3-b']dithiophene)hafnium dimethyl;
dimethylsilanediyl(3-tert-butyl-cyclopentadienyl)(9-fluorenyl)zirconium
dimethyl,
dimethylsilanediyl(3-isopropyl-cyclopentadienyl)(9-fluorenyl)zi-
rconium dimethyl,
dimethylsilanediyl(3-methyl-cyclopentadienyl)(9-fluorenyl)zirconium
dimethyl,
dimethylsilanediyl(3-ethyl-cyclopentadienyl)(9-fluorenyl)zircon-
ium dimethyl,
1-2-ethane(3-tert-butyl-cyclopentadienyl)(9-fluorenyl)zirconium
dimethyl,
1-2-ethane(3-isopropyl-cyclopentadienyl)(9-fluorenyl)zirconium
dimethyl,
1-2-ethane(3-methyl-cyclopentadienyl)(9-fluorenyl)zirconium
dimethyl,
1-2-ethane(3-ethyl-cyclopentadienyl)(9-fluorenyl)zirconium
dimethyl,
dimethylsilandiylbis-6-(3-methylcyclopentadienyl-[1,2-b]-thiophene)dimeth-
yl;
dimethylsilandiylbis-6-(4-methylcyclopentadienyl-[1,2-b]-thiophene)zir-
conium dimethyl;
dimethylsilandiylbis-6-(4-isopropylcyclopentadienyl-[1,2-b]-thiophene)zir-
conium dimethyl;
dimethylsilandiylbis-6-(4-ter-butylcyclopentadienyl-[1,2-b]-thiophene)zir-
conium dimethyl;
dimethylsilandiylbis-6-(3-isopropylcyclopentadienyl-[1,2-b]-thiophene)zir-
conium dimethyl;
dimethylsilandiylbis-6-(3-phenylcyclopentadienyl-[1,2-b]-thiophene)zircon-
ium dimethyl;
dimethylsilandiylbis-6-(2,5-dimethyl-3-phenylcyclopentadienyl-[1,2-b]-thi-
ophene)zirconium dimethyl;
dimethylsilandiylbis-6-[2,5-dimethyl-3-(2-methylphenyl)cyclopentadienyl-[-
1,2-b]-thiophene]zirconium dimethyl;
dimethylsilandiylbis-6-[2,5-dimethyl-3-(2,4,6-trimethylphenyl)cyclopentad-
ienyl-[1,2-b]-thiophene]zirconium dimethyl;
dimethylsilandiylbis-6-[2,5-dimethyl-3-mesitylenecyclopentadienyl-[1,2-b]-
-thiophene]zirconium dimethyl;
dimethylsilandiylbis-6-(2,4,5-trimethyl-3-phenylcyclopentadienyl-[1,2-b]--
thiophene)zirconium dimethyl;
dimethylsilandiylbis-6-(2,5-diethyl-3-phenylcyclopentadienyl-[1,2-b]-thio-
phene)zirconium dimethyl;
dimethylsilandiylbis-6-(2,5-diisopropyl-3-phenylcyclopentadienyl-[1,2-b]--
thiophene)zirconium dimethyl;
dimethylsilandiylbis-6-(2,5-diter-butyl-3-phenylcyclopentadienyl-[1,2-b]--
thiophene)zirconium dimethyl;
dimethylsilandiylbis-6-(2,5-ditrimethylsilyl-3-phenylcyclopentadienyl-[1,-
2-b]-thiophene)zirconium dimethyl;
dimethylsilandiylbis-6-(3-methylcyclopentadienyl-[1,2-b]-silole)zirconium
dimethyl;
dimethylsilandiylbis-6-(3-isopropylcyclopentadienyl-[1,2-b]-sil-
ole)zirconium dimethyl;
dimethylsilandiylbis-6-(3-phenylcyclopentadienyl-[1,2-b]-silole)zirconium
dimethyl;
dimethylsilandiylbis-6-(2,5-dimethyl-3-phenylcyclopentadienyl-[-
1,2-b]-silole)zirconium dimethyl;
dimethylsilandiylbis-6-[2,5-dimethyl-3-(2-methylphenyl)cyclopentadienyl-[-
1,2-b]-silole]zirconium dimethyl;
dimethylsilandiylbis-6-[2,5-dimethyl-3-(2,4,6-trimethylphenyl)cyclopentad-
ienyl-[1,2-b]-silole]zirconium dimethyl;
dimethylsilandiylbis-6-[2,5-dimethyl-3-mesitylenecyclopentadienyl-[1,2-b]-
-silole]zirconium dimethyl;
dimethylsilandiylbis-6-(2,4,5-trimethyl-3-phenylcyclopentadienyl-[1,2-b]--
silole)zirconium dimethyl;
[dimethylsilyl(tert-butylamido)][(N-methyl-1,2-dihydrocyclopenta[2,1-b]in-
dol-2-yl)]titanium dimethyl;
[dimethylsilyl(tert-butylamido)][(6-methyl-N-methyl-1,2-dihydrocyclopenta-
[2,1-b]indol-2-yl)]titanium dimethyl;
[dimethylsilyl(tert-butylamido)][(6-methoxy-N-methyl-1,2-dihydrocyclopent-
a[2,1-b]indol-2-yl)]titanium dimethyl;
[dimethylsilyl(tert-butylamido)][(N-ethyl-1,2-dihydrocyclopenta[2,1-b]ind-
ol-2-yl)]titanium dimethyl;
[dimethylsilyl(tert-butylamido)][(N-phenyl-1,2-dihydrocyclopenta[2,1-b]in-
dol-2-yl)]titanium dimethyl;
[dimethylsilyl(tert-butylamido)][(6-methyl-N-phenyl-1,2dihydrocyclopenta[-
2,1-b]indol2-yl)]titanium dimethyl;
[dimethylsilyl(tert-butylamido)][(6-methoxy-N-phenyl-1,2-dihydrocyclopent-
a[2,1-b]indol2-yl)]titanium dimethyl;
[dimethylsilyl(tert-butylamido)][(N-methyl-3,4-dimethyl-1,2-dihydrocyclop-
enta[2,1-b]indol-2-yl)]titanium dimethyl;
[dimethylsilyl(tert-butylamido)][(N-ethyl-3,4-dimethyl-1,2-dihydrocyclope-
nta[2,1-b]indol-2-yl)]titanium dimethyl;
[dimethylsilyl(tert-butylamido)][(N-phenyl-3,4-dimethyl-1,2-dihydroclopen-
ta[2,1-b]indol-2-yl)]titanium dimethyl; as well as the
corresponding dichloro, hydrochloro and dihydro compounds and the
corresponding .eta..sup.4-butadiene compounds.
When A is N(R.sup.8), a suitable class of metallocene complexes (A)
for use in the catalysts complexes of the invention comprises the
well-known constrained geometry catalysts, as described in EP-A-0
416 815, EP-A-0 420 436, EP-A-0 671 404, EP-A-0 643 066 and
WO-A-91/04257.
A further preferred class of transition metal organometallic
catalyst compounds is a late transition metal complex of formula
(XII) or (XIII): L.sup.aM.sup.aX.sup.ap.sup.a (XII)
L.sup.aM.sup.aA.sup.a (XIII) wherein M.sup.a is a metal belonging
to Group 8, 9, 10 or 11 of the Periodic Table of the Elements (new
IUPAC notation);
L.sup.a is a bidentate or tridentate ligand of formula (XIV):
##STR00015## wherein: Q is a C.sub.1 C.sub.50 bridging group
linking E.sup.1 and E.sup.2, optionally containing one or more
atoms belonging to Groups 13 17 of the Periodic Table; E.sup.1 and
E.sup.2, the same or different from each other, are elements
belonging to Group 15 or 16 of the Periodic Table and are bonded to
said metal M.sup.a; the substituents R.sup.a1, equal to or
different from each other, are selected from the group consisting
of hydrogen, linear or branched, saturated or unsaturated C.sub.1
C.sub.20 alkyl, C.sub.3 C.sub.20 cycloalkyl, C.sub.6 C.sub.20 aryl,
C.sub.7 C.sub.20 alkylaryl and C.sub.7 C.sub.20 arylalkyl radicals,
optionally containing one or more atoms belonging to groups 13 17
of the Periodic Table of the Elements (such as B, Al, Si, Ge, N, P,
O, S, F and Cl atoms); or two R.sup.a1 substituents attached to the
same atom E.sup.1 or E.sup.2 form a saturated, unsaturated or
aromatic C.sub.4 C.sub.7 ring, having from 4 to 20 carbon atoms;
m.sup.a and n.sup.a are independently 0, 1 or 2, depending on the
valence of E.sup.1 and E.sup.2, so to satisfy the valence number of
E.sup.1 and E.sup.2; q.sup.a is the charge of the bidentate or
tridentate ligand so that the oxidation state of
M.sup.aX.sup.a.sub.pX.sup.a'.sub.s or M.sup.aA.sup.a is satisfied,
and the compound (XII) or (XIII) is overall neutral; X.sup.a, the
same or different from each other, are monoanionic sigma ligands
selected from the group consisting of hydrogen, halogen, R.sup.a,
OR.sup.a, OSO.sub.2CF.sub.3, OCOR.sup.a, SR.sup.a, --NR.sub.2 and
PR.sup.a.sub.2 groups, wherein the R.sup.a substituents are linear
or branched, saturated or unsaturated, C.sub.1 C.sub.20 alkyl,
C.sub.3 C.sub.20 cycloalkyl, C.sub.6 C.sub.20 aryl, C.sub.7
C.sub.20 alkylaryl or C.sub.7 C.sub.20 arylalkyl radicals,
optionally containing one or more atoms belonging to groups 13 17
of the Periodic Table of the Elements (new IUPAC notation), such as
B, N, P, Al, Si, Ge, O, S and F atoms; or two X.sup.a groups form a
metallacycle ring containing from 3 to 20 carbon atoms; the
substituents X.sup.a are preferably the same; p.sup.a is an integer
ranging from 0 to 3, so that the final compound (XII) or (XIII) is
overall neutral; and A.sup.a is a .pi.-allyl or a .pi.-benzyl
group.
Non limiting examples of late transition metal complexes are those
described in WO 96/23010, WO 97/02298, WO 98/40374 and J. Am. Chem.
Soc. 120:4049 4050, 1998. Brookhart et al, J. Am. Chem. Soc. 1995,
117, 6414 and Brookhart et al, J. Am. Chem. Soc., 1996, 118, 267,
Brookhart et al, J. Am. Chem. Soc. 1998, 120, 4049, Gibson et al,
Chem. Commun. 1998, 849, WO 96/27439 and Chem. Ber./Recl. (1997),
130(3), 399 403. The organometallic compounds and the salts
according to the invention exert good activities as cocatalysts in
olefin polymerization process; moreover, they are easy to prepare
and do not lead to the release of undesired by-products after the
metallocene activation. Further they are stable and produce stable
catalyst compositions under polymerization conditions.
The molar ratio between the component (B) and the transition metal
organometallic compound (A), calculated as the molar ratio between
the metal Mt of the Lewis acid and the metal of the transition
metal organometallic catalyst compound, preferably ranges from 10:1
to 1:10, more preferably from 2:1 to 1:2, and even more preferably
is about 1:1.
According to the invention, component (B) of the catalyst system
can suitably comprise a mixture of two or more organometallic
compounds or salts of the invention. Moreover, component (B) can be
used in combination with other compatible cocatalysts known in the
state of the art, such as alumoxane compounds.
The catalyst system of the invention may also comprise one or more
aluminum compounds of formula AlR.sup.10.sub.3-zW.sub.z, acting as
scavenger, wherein R.sup.10 can be C.sub.1 C.sub.10 alkyl, alkenyl
or alkylaryl radicals, optionally containing one or more Si or Ge
atoms, z is 0, 1 or 2 or a non integer number ranging from 0 to 2;
W is hydrogen, chlorine, bromine or iodine; non-limiting examples
of aluminum compounds are trimethylaluminum (TMA),
tris(2,4,4-trimethyl-pentyl)aluminum (TIOA),
tris(2-methyl-propyl)aluminum (TIBA),
tris(2,3,3-trimethyl-butyl)aluminum,
tris(2,3-dimethyl-hexyl)aluminum, tris(2,3-dimethyl-butyl)aluminum,
tris(2,3-dimethyl-pentyl)aluminum,
tris(2,3-dimethyl-heptyl)aluminum,
tris(2-methyl-3-ethyl-pentyl)aluminum and
tris(2-ethyl-3,3-dimethyl-butyl).
Another example of compound that can act as scavenger are alumoxane
compounds containing at least one group of the type:
##STR00016## wherein the R.sup.11 substituents, which may be the
same or different, are described above.
In particular, alumoxanes of the formula:
##STR00017## can be used in the case of linear compounds, wherein
n.sup.1 is 0 or an integer from 1 to 40 and the R.sup.11
substituents are defined as above, or alumoxanes of the
formula:
##STR00018## can be used in the case of cyclic compounds, wherein
n.sup.2 is an integer from 2 to 40 and the R.sup.11 substituents
are defined as above.
Examples of alumoxanes suitable as scavenger according to the
present invention are methylalumoxane (MAO),
tetra-(isobutyl)alumoxane (TIBAO),
tetra-(2,4,4-trimethyl-pentyl)alumoxane (TIOAO),
tetra-(2,3-dimethylbutyl)alumoxane (TDMBAO) and
tetra-(2,3,3-trimethylbutyl)alumoxane (TTMBAO).
Particularly interesting alumoxanes are those disclosed in WO
99/21899.
The catalyst system of the invention may be formed prior to its
introduction into a polymerization reactor or in situ in the
reactor, by contacting the above-described components (A), (B) and
optionally an alkylating agent.
According to an embodiment of the invention, components (A), (B)
and optionally an alkylating agent are first contacted and then
introduced into the reactor, wherein separately an aluminum
compound AlR.sup.10.sub.3-zW.sub.z, or an alumoxane has been
introduced. Alternatively, components (A), (B) and optionally an
alkylating agent and said aluminum compound
AlR.sup.10.sub.3-zW.sub.z or said alumoxane may be contacted
together prior to their introduction into the reactor.
The catalysts system of the present invention can be used on inert
supports. This may be achieved by depositing said transition metal
organometallic catalyst compound (A), or the product of the
reaction thereof with the component (B), or the component (B) and
subsequently said transition metal organometallic compound before
or after the optional treatment with said alkylating agent, on
inert supports such as silica, alumina, styrene/divinylbenzene
copolymers, polyethylene or polypropylene.
The thus obtained solid compound can be suitably used in gas phase
polymerization.
The catalysts of the present invention can be used in the
polymerization reactions of olefins.
Therefore, according to a further object, the invention provides a
process for the polymerization of one or more olefins comprising
contacting one or more olefins under polymerization conditions in
the presence of a catalyst system as described above.
Olefins which can be polymerized with the process of the present
invention are, for instance, .alpha.-olefins of formula
CH.sub.2.dbd.CHR, wherein R is hydrogen or a C.sub.1 C.sub.20 alkyl
radical.
The catalysts according to the present invention can be
conveniently used in the homopolymerization of ethylene, in
particular for the preparation of HDPE, and in the copolymerization
of ethylene, in particular for the preparation of LLDPE. Suitable
comonomers in ethylene copolymers are .alpha.-olefins of formula
CH.sub.2.dbd.CHR', wherein R' is a linear, branched or cyclic
C.sub.1 C.sub.20 alkyl radical or cycloolefins. Examples of such
olefins are propylene, 1-butene, 1-pentene, 4-methyl-1-pentene,
1-hexene, 1-octene, allyl-cyclohexane, cyclopentene, cyclohexene,
norbornene and 4,6-dimethyl-1-heptene.
Further suitable comonomers in said ethylene copolymers are
polyenes, in particular conjugated or non-conjugated, linear or
cyclic dienes, such as 1,4hexadiene, isoprene, 1,3-butadiene,
1,5-hexadiene and 1,6-heptadiene.
The catalysts of the invention can be suitably used in propylene
homopolymerization, or copolymerization in particular for the
production of isotactic polypropylene.
Moreover, the catalysts of the invention can be suitably used in
the preparation of elastomeric copolymers of ethylene with
.alpha.-olefins of formula CH.sub.2.dbd.CHR'', wherein R'' is a
C.sub.1 C.sub.10 alkyl radical, such as propylene, 1-butene,
4-methyl-1-pentene, 1-hexene and 1-octene; said copolymers may
optionally contain minor proportions of units deriving from
polyenes.
According to a further embodiment, the catalysts according to the
present invention are used in the preparation of cycloolefin
polymers. Monocyclic and polycyclic olefin monomers can be either
homopolymerized or copolymerized, also with linear olefin
monomers.
The polymerization processes of the present invention can be
carried out in liquid phase, optionally in the presence of an inert
hydrocarbon solvent, or in gas phase. Said hydrocarbon solvent can
be either aromatic (such as toluene) or aliphatic (such as propane,
hexane, heptane, isobutane, cyclohexane and
2,2,4-trimethylpentane).
The polymerization temperature preferably ranges from 0.degree. C.
to 250.degree. C.; in the preparation of HDPE and LLDPE, it is
preferably comprised between 20.degree. C. and 150.degree. C. and,
more particularly between 40.degree. C. and 90.degree. C.; in the
preparation of elastomeric copolymers, it is preferably comprised
between 0.degree. C. and 200.degree. C., and more preferably
between 20.degree. C. and 100.degree. C. The molecular weight of
the polymers can be varied simply by varying the polymerization
temperature, the type or the concentration of the catalyst
components, or by using molecular weight regulators, such as
hydrogen.
The molecular weight distribution can be varied by using mixtures
of different metallocene complexes or by carrying out the
polymerization in several stages which differ in the polymerization
temperature and/or the concentrations of molecular weight
regulator.
The polymerization yield depends on the purity of the transition
metal organometallic catalyst compound (A) in the catalyst,
therefore, said compound can be used as such or can be subjected to
purification treatments before use.
The following examples are given for illustrative and not limiting
purposes.
GENERAL PROCEDURES AND CHARACTERIZATIONS
All operations were performed under nitrogen by using conventional
Schlenk-line techniques. Solvents were purified by degassing with
N.sub.2 and passing over activated (8 hours, N.sub.2 purge,
300.degree. C.) Al.sub.2O.sub.3, and stored under nitrogen. Indole
(Aldrich, purity 98% or Fluka, purity 99%), N-methylindole
(Aldrich, purity 97%), N-methylpyrrole (Aldrich, purity 99%),
NEt.sub.3 (Aldrich, 99.5%) and B(C.sub.6F.sub.5).sub.3 (Boulder
Scientific Company) were used as received.
.sup.1H-NMR and .sup.13C-NMR
The proton and carbon spectra of the compounds were obtained using
a Bruker DPX 200 spectrometer operating in the Fourier transform
mode at room temperature at 200.13 MHz and 50.33 MHz respectively.
The samples were dissolved in CD.sub.2Cl.sub.2 or C.sub.6D.sub.6.
As reference the residual peak of CHDCl.sub.2 or C.sub.6HD.sub.5 in
the .sup.1H spectra (5.35 ppm and 7.15 ppm, respectively) and the
peak of the solvent in the .sup.13C spectra (53.80 ppm for
CD.sub.2Cl.sub.2 and 128.00 ppm for C.sub.6D.sub.6) were used.
Proton spectra were acquired with a 15.degree. pulse and 2 seconds
of delay between pulses; 32 transients were stored for each
spectrum. The carbon spectra were acquired with a 45.degree. pulse
and 6 seconds of delay between pulses; about 512 transients were
stored for each spectrum. CD.sub.2Cl.sub.2 (Aldrich, 99.8% atom D)
was used as received, while C.sub.6D.sub.6 (Aldrich, 99% atom D)
was dried over activated 4 A.degree. molecular sieves before use.
Preparation of the samples was carried out under nitrogen using
standard inert atmosphere techniques.
SYNTHESIS OF THE ORGANOMETALLIC BORON COMPOUNDS
EXAMPLE 1
Synthesis of 2-[tris(pentafluorophenyl)borane]-3H-1-methylindole
[A-1]
##STR00019##
A yellow solution of 1-methylindole (97%, 0.78 g, MW=131.18, 5.8
mmol) in 10 ml of dichloromethane was added at room temperature to
a white suspension of B(C.sub.6F.sub.5).sub.3 (99.4%, 2.97 g,
MW=511.99, 5.8 mmol) in 10 ml of dichloromethane in a 25 mL Schlenk
flask. The resulting orange solution was stirred at room
temperature for ten days and analyzed by .sup.1H NMR at different
times. During this time the color of the solution turned from
orange to dark bordeaux; NMR analyses showed a slow conversion of
the starting 1-methylindole to the product. The solvent was
evaporated in vacuum and the obtained solid was suspended in a 9/1
pentane/dicloromethane mixture and filtered. The residue on the
frit was a fuchsia solid (3.27 g, yield 87.8%).
The product was completely characterized by .sup.1H NMR, .sup.13C
NMR, DEPT (Distorsionless Enhancement by Polarization Transfer),
NOESY (Nuclear Overhauser Enhancement Spectroscopy), COSY
(Correlation Spectroscopy), HSQC (Heteronuclear Single Quantum
Coherence) and HMBC (Heteronuclear Multiple Bond Correlation)
analyses.
.sup.1H NMR (CD.sub.2Cl.sub.2, .delta., ppm): 3.77 (s, 3H,
N--CH.sub.3); 4.59 (broad AB system, 2H3,H3'); 7.47 7.69 (m, 4H,
Ar).
.sup.1H NMR (C.sub.6D.sub.6, .delta., ppm): 2.84 (s, 3H,
N--CH.sub.3); 4.04 (broad AB system, 2H, H3,H3'); 6.42 6.51 (m, 1H,
H7); 6.83 6.98 (m, 3H, Ar).
.sup.13C NMR (CD.sub.2Cl.sub.2, .delta., ppm): 36.55 (CH.sub.3);
48.33 (C3); 113.59 (C7); 125.22 (C4); 128.97 (C5 or C6); 129.22 (C6
or C5); 134.18 (C3a); 147.06 (C7a); 214.34 217.43 (m, C2). melting
point 126.7.degree. C. 127.8.degree. C.
EXAMPLE 2
Synthesis of
tris(pentafluorophenyl)-(1-methylindol-2-yl)-borate(1-)triethylammonium
[A-2]
##STR00020##
A colorless solution of triethylamine (99.5%, 0.167 g, MW=101.19,
1.6 mmol) (dichloromethane, 6 mL) was added at room temperature to
a bordeaux solution of
2-[tris(pentafluorophenyl)borane]-3H-1-methylindole (1.048 g,
MW=643.16, 1.6 mmol) (dichloromethane, 4 mL) in a 10 mL Schlenk
flask. The resulting solution was stirred at room temperature for
an hour and its color turned from the initially orange to yellow.
Then the solvent was removed in vacuum to give a yellow solid as
product, 1.11 g, yield 93.2%).
.sup.1H NMR (CD.sub.2Cl.sub.2, .delta., ppm): 1.03 (t, 9H, J=7.24
Hz, N(CH.sub.2CH.sub.3).sub.3); 2.60 (q, 6H, J=7.24 Hz,
N(CH.sub.2CH.sub.3).sub.3); 3.40 (bs, 1H, NH); 3.51 (s, 3H,
N--CH.sub.3); 6.19 (s, 1H, H3); 6.95 7.13 (m, 2H, H5,H6); 7.23 7.29
(m, 1H, H7); 7.41 7.48 (m, 1H, H4).
.sup.13C NMR (CD.sub.2Cl.sub.2, .delta., ppm): 8.56
(N(CH.sub.2CH.sub.3).sub.3); 31.84 (N--CH.sub.3); 47.32
(N(CH.sub.2CH.sub.3).sub.3); 104.75 (C3); 109.35 (C7); 118.29 and
118.35 (C4 and C5 or C6); 119.19 (C6 or C5); 128.79 (C3a); 139.47
(C7a).
EXAMPLE 3
Synthesis of 2-[tris(pentafluorophenyl)borane]-5H-1-methylpyrrole
[A-3]
##STR00021##
A light yellow solution of 1-methylpyrrole (99%, 0.503 g, MW=81.12,
6.1 mmol) (dichloromethane, 10 mL) was added at room temperature to
a white-gray suspension of B(C.sub.6F.sub.5).sub.3 (99.4%, 3.18 g,
MW=511.99, 6.2 mmol) (dichloromethane, 10 mL). The resulting orange
cloudy solution was stirred at room temperature for three days and
then the solvent was removed under reduced pressure. The obtained
orange powder was suspended with a 1/2 dichloromethane/pentane
mixture and filtered. The filtrate was a dark pink solid (the
desired product together with unidentified species), whereas the
residue on the frit was a very light yellow powder (2.42 g of the
desired product, yield 66.5%).
.sup.1H NMR (CD.sub.2Cl.sub.2, .delta., ppm): 3.55 (s, 3H,
CH.sub.3); 4.70 (bs, 2H, H5, H5'); 6.91 (bs, 1H, H3); 7.42 (d,
J=5.87 Hz, 1H, H4).
.sup.13C NMR (CD.sub.2Cl.sub.2, .delta., ppm): 38.12 (CH.sub.3);
69.81 (C5); 108.42 (C2); 137.33 (C3); 146.06 (C4). Melting point
116.6.degree. C. 118.2.degree. C.
EXAMPLE 4
Synthesis of
tris(pentafluorophenyl)-(1-methypyrrol-2-yl)-borate(1-)
triethylammonium [A-4]
##STR00022##
A colorless solution of triethylamine (99.5%, 0.167 g, MW=101.19,
1.6 mmol) (dichloromethane, 6 mL) was added at room temperature to
an orange solution of
2-[tris(pentafluorophenyl)borane]-5H-1-methylpyrrole [A-3] (1.048
g, MW=643.16, 1.6 mmol) (dichloromethane, 6 mL) in a 25 mL Schlenk
flask. The resulting light yellow solution was stirred at room
temperature for an hour. Then the solvent was removed under reduced
pressure to give a white-gray solid as product (0.892 g, yield
97.9%).
.sup.1H NMR (CD.sub.2Cl.sub.2, .delta., ppm): 1.22 (t, 9H, J=7.34
Hz, N(CH.sub.2CH.sub.3).sub.3); 3.03 (q, 6H, J=7.34 Hz,
N(CH.sub.2CH.sub.3).sub.3); 3.32 (s, 3H, N--CH.sub.3); 5.76 (bd,
1H, J=2.64 Hz, H3); 5.96 (d, 1H, J=3.23 Hz, H4); 6.10 (bs, 1H, NH);
6.64 (bs, 1H, H5).
.sup.13C NMR (CD.sub.2Cl.sub.2, .delta., ppm): 8.82
(N(CH.sub.2CH.sub.3).sub.3); 35.94 (N--CH.sub.3); 47.32
(N(CH.sub.2CH.sub.3).sub.3); 104.40 (C4); 111.85 (C3); 122.95 (C5),
146.20 (C2).
Synthesis of bis(indenyl)zirconium dimethyl
29.6 mL of a solution of MeLi 1.6 M in Et.sub.2O (47.4 mmol) were
added at room temperature to a solution of 3 g of indene (23.7
mmol, Aldrich, 91.8 %) in 30 mL of Et.sub.2O, over a period of
about 5 minutes (exothermic reaction). The mixture was stirred for
30 minutes to give an orange solution.
2.76 g of ZrCl.sub.4 (11.84 mmol) were slurried in 30 mL of
pentane. The ZrCl.sub.4 slurry in pentane was quickly added to the
Li salt solution in Et.sub.2O (exothermic reaction). The resulting
reaction mixture was stirred for 2 hours and then brought to
dryness under reduced pressure. The light brown solid obtained was
extracted with 100 mL of pentane (Soxhlet, 4.5 hours) and then the
filtrate was evaporated to dryness under reduced pressure to give
3.2 g (77% yield) of a light yellow solid, which was characterized
by .sup.1H NMR as pure Ind.sub.2ZrMe.sub.2.
.sup.1H-NMR (C.sub.6D.sub.6, .delta., ppm): -0.78 (s, 6H,
Zr--CH.sub.3), 5.62 (t, 2H, Cp-H(2)), 5.80 (d, 4H, Cp-H(1,3)); 6.87
6.92 (m, 4H, Ar), 7.19 7.23 (m, 4H, Ar).
Preparation of the Catalyst System
0.1 .mu.mol of bis(indenyl)zirconium dimethyl prepared as reported
above, was dissolved in 2 mL of toluene in a 10 mL Schlenk under
nitrogen atmosphere and then the cocatalyst indicated in table 1 in
2 mL toluene was quickly added (Zr/cocat molar ration 1:1.1).
Polymerization Examples 5 8
Ethylene Polymerization
Ethylene polymerizations were carried out in a 260-mL Buchi glass
autoclave equipped with magnetic stirrer, thermocouple and feeding
line for the monomer, purified with nitrogen and kept in a
thermostatic bath. Under ethylene purge, heptane (100 mL) and
Al(i-Bu).sub.3 (0.1 mmol) were introduced, the temperature was
brought to 80.degree. C. and the reactor vented to remove residual
nitrogen, then pressurized with ethylene up to 0.5 bar-g. The
catalytic system, prepared as described above, was siphoned into
the reactor by means of a Teflon cannula, and the ethylene partial
pressure was raised to 4 bar-g. The polymerization was carried out
at 80.degree. C. for 15 minutes, by maintaining a constant ethylene
partial pressure, then stopped by degassing the reactor and by
adding 2 mL of methanol. The polymer was precipitated with 200 mL
of acetone, filtered, washed with acetone and dried overnight at
60.degree. C. reduced pressure. The polymerization results are
reported in table 1.
TABLE-US-00001 TABLE 1 Example Cocatalyst yield (g)
kg.sub.PE/(mmol.sub.Zr .times. h) 5 A-1 1.90 7.6 6 A-2 1.81 7.2 7
A-3 2.15 8.6 8 A-4 6.87 27.5
* * * * *